CN105419392B - The diffractive pigment manufactured by fluidized-bed chemical vapor deposition method - Google Patents

The diffractive pigment manufactured by fluidized-bed chemical vapor deposition method Download PDF

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Publication number
CN105419392B
CN105419392B CN201510819522.9A CN201510819522A CN105419392B CN 105419392 B CN105419392 B CN 105419392B CN 201510819522 A CN201510819522 A CN 201510819522A CN 105419392 B CN105419392 B CN 105419392B
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micro
structural
core
dielectric
layer
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CN105419392A (en
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阿尔博特·阿革帝亚
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Only Yahweh Communication Technology Co Ltd
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Viavi Solutions Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0051—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • C09C2200/1008—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2 comprising at least one metal layer adjacent to the core material, e.g. core-M or M-core-M
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2210/00—Special effects or uses of interference pigments
    • C09C2210/30—A layer or the substrate forming a grating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2210/00—Special effects or uses of interference pigments
    • C09C2210/40—Embossed layers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to a kind of micro-structural pigment including dielectric core, which has diffraction grating.The micro-structural dielectric core is packaged with one or more encapsulated layers, deposits the encapsulated layer in fluid bed using chemical vapour deposition technique.The fluidization conditions provide uniform and very conformal encapsulated layer.

Description

The diffractive pigment manufactured by fluidized-bed chemical vapor deposition method
The application is the applying date for August in 2012 16 days, Application No. 201210291218.8 and entitled The divisional application of the Chinese invention patent application of " diffractive pigment manufactured by fluidized-bed chemical vapor deposition method ".
Technical field
The present invention relates generally to thin film flakes, and relate more specifically to the manufacturing method of micro-structural pigment flakes.
Background technology
It has developed professional pigment and has been used for the security devices printed in Application in Anti-counterfeiting, such as banknote, high-value items Packaging, container strip of paper used for sealing, and even it has been applied directly to commercial good.For example, 20 dollars of Federal Reserve bank note mesh Before use optically variable ink.The number " 20 " for being printed on the positive lower right corner of bank note changes face with the variation at visual angle Color.This is a kind of apparent security devices.Gamut effect is cannot to be replicated by common color copy machine, and receives bank note People can see whether the coloured shifting security feature of the bank note, with determine the bank note authenticity.
The file of other high values has used similar measure with article.For example, luster pigment or diffractive pigment are used for Coating and ink, the coating and ink are applied directly to article, such as share certificate, passport, and original product is packed or for quilt It is applied to the strip of paper used for sealing of article.Since imitator constantly becomes more complicated, it is therefore desirable to more be difficult to the anti-fake spy forged Property.
A kind of method for anti-counterfeit is that microcosmic symbol is used on multilayer gamut pigment flakes.In the multilayer gamut pigment flakes at least One layer the upper surface of forms the symbol for example, by the localized variation of the optical characteristics of reflectivity.The multilayer gamut pigment flakes can have There are full dielectric design or inter metal dielectric design.These symbols can be stamped in the pigment by mechanical means or embossment Or it etches or is formed by laser means.
Micro-structural piece with diffraction grating or symbol generally requires additional layer, such as provides gamut effect Layer.A kind of traditional method is to coat (roll-to roll coating) using reel-to-reel.A roll of polymeric base material piece (also referred to as " mesh (web) ") is coated by crystallizing field, and with one or more layers film layer.It can make the polymerization Object substrate is rolled up repeatedly back and forth through crystallizing field.Then, the coating of deposition is separated with the polymeric substrates, and is formed to Piece.But the deposition substrate that this pigment needs to grow very much is mass produced, and in this case, reel-to-reel technology is Inconvenient.
Accordingly, it is desirable to provide a kind of multi-layer pigments piece that manufacture for the limitation for overcoming techniques discussed above is micro-structural Method.
Full dielectric interference structure can be formed by the dielectric layer with different refractive index.These layers can be utilized The various optical variable effects for combining to realize needs.Whole dielectric pigment flakes can be micro-structural, they can be wrapped It includes for the mark of anti-fake purpose or with the diffraction grating for providing optical variable effect.
It is a further object to provide for manufacturing the effective ways of complete dielectric micro-structural piece.
The content of the invention
The present invention provides a kind of methods for forming micro-structural pigment flakes.This method includes providing to fluid bed Micro-structural dielectric core, and the micro-structural dielectric is encapsulated by chemical vapour deposition technique in the fluid bed Core, so as to form the encapsulated layer for encapsulating the micro-structural dielectric core.
Another aspect of the present invention provides complete dielectric diffractive pigment piece, including diffraction core and one layer or more The very conformal encapsulated layer of layer, wherein when the piece is located in the fluid bed, the encapsulated layer is provided using chemical vapour deposition technique.
Description of the drawings
The present invention is described more fully by reference to illustrating the attached drawing of each preferred embodiment of the invention, In：
Fig. 1 is the schematic diagram for showing film interference；
Fig. 2 and Fig. 3 is the schematic diagram for showing diffraction interference；
Fig. 4 is shown in the schematic diagram of the interference in the dielectric diffractive pigment of three floor heights/low high refractive index；
Fig. 5 A are the flow charts of the method for the micro-structural pigment flakes of manufacture；
Fig. 5 B are the schematic diagrames for showing the piece that makes paints；
Fig. 6 is for the schematic diagram of the fluid bed in fluidized-bed chemical vapor deposition (FBCVD)；
Fig. 7 A to Fig. 7 D are scanning electron microscope (SEM) microphotos of diffractive pigment piece；
Fig. 8 A to Fig. 8 C are transmission electron microscope (TEM) cross sectional images of common case chip；
Fig. 9 is scanning transmission electron microscope (STEM) image at piece edge；With
Figure 10 is drawn by the result of the elemental analysis of the spectrum in the region marked in the STEM images that are shown in Fig. 9 Figure.
Specific embodiment
Multilayer optical piece can provide diffraction optics effect due to the diffraction micro structural formed on the surface of the piece； And the optical interference caused by layer structure, it is capable of providing gamut effect.The diffraction micro structural can be in dielectric core It is then packaged by middle formation with one or more layers encapsulated layer.So that need coat all or at least to the greatest extent can be more Ground and the micro-structure of diffraction core are conformal, to generate based on the film interference for combining stratiform coating and as caused by the micro-structure The optical effect of the needs of diffraction interference.
When all dielectric optical design is formed rather than formed in the plane on raster-like surface, thus The micro-structural piece generated shows the color change occurred with visual angle change, this is because film interference and diffraction interference Caused by simultaneously.Only when all interfaces between high index of refraction and the dielectric material layer of low-refraction have raster-like Micro-structure, the combination of interference effect just can effectively occur.In the case of encapsulated layer is not conformal, diffraction effect lose or Person's at least effect is seriously attenuated, and pigment only or largely shows film interference.Therefore, selection is for can be with The encapsulation technology for replicating the diffraction core sheet of the micro-structure in encapsulated layer is important.In other words, sedimentary should be with the core The original microstructure of lamination is highly conformable.
When the border between light wave runs into the trnaslucent materials with different refractive index, film interference occurs, so as to Light wave is caused to be divided into back wave and transmitted wave.When second of material has the refractive index higher than the first material, the reflected beams It experienced the phase shift of 180 degree.Typical example is soap bubble.Cross section lathery (n=1.33), the fertilizer is shown in Fig. 1 Soap bubble is filled by air and surrounded (n=1) by air.First transmitted wave is transferred to internal bubble/Air Interface, so as to again It is divided into back wave and transmitted wave.It repeats the process and generates an infinite number of back wave and transmitted wave.For anti-by soap bubble The different wave length of the white incident light for the charming color of generation observed in the light penetrated, constructive and destructive interference condition are Different.
When transmission light wave runs into the obstacle similarly sized with its wavelength, diffraction interference or diffraction occurs.If the obstacle It is periodic, the energy of some wavelength is dispersed to different discrete direction (diffraction progression).This optical device is referred to as " diffraction grating ".
Diffraction grating is a kind of optical module, the reflecting element that it is separated by the distance of the wavelength by being equivalent to incident light Or the component of transmissive element is made.When monochromatic light is when incident on grating, it is diffraction in discrete direction.As shown in Figure 2, In grating, diffraction light sources of each grating groove as one small slit shape.It combines to be formed by the light of each groove diffraction Before diffracted wave.As shown in Fig. 2, to be not orthogonal to, the angle of grating surface generates zero level in the light of grating surface incidence or minute surface is anti- It penetrates.Diffraction grating generates first order diffracted beam (negative one grade to positive level-one) in the both sides of the zero order reflection.Similarly, higher Angle, the diffraction light of the second level and higher level can be generated.As shown in figure 3, diffraction can also occur in transmission.
Compared with schematical three layers full dielectric pigment of the HLH types surrounded by air, film is further discussed and is spread out The combination of interference effect is penetrated, wherein H represents high refractive index layer and L expression tools with the refractive index more than 1.65 and less than 2.7 There is the low-index layer of the refractive index less than or equal to 1.65 and more than 1.3.Fig. 4 schematically show pigment air/ The minute surface light beam and some diffracted beams that high index of refraction and high index of refraction/low-refraction interface boundary are reflected and/or transmitted.It is real On border, incident beam is reflected according to the law of reflection or diffraction, and the transmitted light beam can be in layer with minute surface direction Or passed through with diffraction direction.Only consider the first transmitted light beam, it is then reflected by high index of refraction and low-index layer by height Rate/low-refraction interface reflection.Second internal reflection from low-refraction/high index of refraction interface as the dotted line arrows, Without considering their track.Subscript " s " and " d " refer respectively to the light beam of mirror-reflection and diffraction reflection or transmission.R and T refer to Reflection or transmitted light beam, H and L refer to high index of refraction dielectric layer and low-refraction dielectric layer.For example, this term, RLs tables Show by the minute surface light beam of the boundary layer reflection of high index of refraction/low-refraction, and THd-expression is saturating by air/high index of refraction interface The diffracted beam penetrated.
Display only by air/high index of refraction interface (RHs) first specular reflectance beam and be marked as The specular transmission (H) of THsRLsTHs/reflection (L)/transmission (H) works to mirror-reflection.It note that this light path is equivalent to The path of pure film interference.
As for the ripple in terms of diffraction, considering diffraction interaction of experience.The reflected beams labeled as RHd are unique one A light beam from air/high index of refraction interface.It is through this layer and other three ripples for having been subjected to a diffraction THdRLsTHs, THsRLdTHs and THsRLsTHd.These three ripples interfere with each other and with the wave interference labeled as RHd.It please note The light path of meaning, the involved light path of definition interference and minute surface light beam is different.
Specular transmission light beam (shown in double-head arrow) from high/low refractive index interfaces, follows air/high index of refraction before The minute surface and diffraction interference of interface, are respectively labeled as THsTLsAnd THdTLs。
Diffraction transmitted light beam (shown in double-head arrow) from high/low refractive index interfaces, follows air/high index of refraction before The minute surface and diffraction interference of interface, are respectively labeled as THsTLdAnd THdTLd。
Even if the considerations of some initial to these ripples is complicated.For example, it only shows anti-from antiradar reflectivity/height First the reflected beams at rate interface are penetrated, follow the minute surface from low-index layer and high refractive index layer and diffraction transmission before. When light beam is by transmission and with the interface of air and/or at low high refractive index interfaces, second high rolled over into and out this When penetrating rate material, each in these light beams itself will follow multiple compound interlayers and layer from minute surface and diffraction interference Internal reflection and transmission.
Fig. 4 is shown if the laminated coating meets the light path occurred during the rasterisation micro-structure of core thin slice very much. When encapsulated layer and the not conformal situation of the diffraction structure of core, diffraction effect does not occur, and pigment mainly shows film interference.
It has been observed that traditional encapsulation technology, such as sol-gel method or wet chemistry method, the colloidal sol-solidifying Glue method includes the decomposition of metal alkoxide and subsequent drying and annealing in presence of water；The wet chemistry method is based on from gold Belong to the precipitation in the aqueous solution of salt, be then dried and roast；The above method cannot all generate fully conformal coating.We Experiment show that fluidized-bed chemical vapor deposition technology (FBCVD) improves micro-structural dielectric prefabricated film (core) The conformal performance of encapsulated layer.Result of the test is further discussed with reference to figure 7A-10.
With reference to figure 5A, forming the method for micro-structural pigment flakes includes core offer step 210 and encapsulation step 220, Step 210 wherein is provided in core, micro-structural dielectric core is provided into fluidized bed, wherein in encapsulation step 220, Micro-structural dielectric core is packaged with one or more layers encapsulated layer for encapsulating the micro-structural dielectric core； Using chemical vapour deposition technique, while micro-structural core is in fluid bed.Core offer step 210 can be included in micro- The step of step 212 of deposit dielectrics coating in the deposition substrate of structuring, disengaging (removing) dielectric coating 214, and the dielectric coating is broken into the step 216 of the multiple cores including the micro-structural dielectric core.
Micro-structural pigment flakes can include dielectric core and one or more encapsulated layers.Piece core can have shape Into micro-structure wherein, and by depositing one or more dielectric film layer (examples in micro-structural deposition substrate Such as plastic film) deposition step 212 manufactured, by the film layer from substrate separation 214, and process the separated film Layer, such as pass through milling and the destruction step 216 for being divided into prefabricated film.In encapsulation step 220, with film layer to prefabricated film Or core is packaged.It is alternatively possible to additional encapsulation step 222 is carried out, to generate more than one encapsulated layer.Thus produce Raw pigment flakes are generally about 5-100 microns wide, and generally about 20-100 microns wide.
Core can include single dielectric layer or multiple electricity including having the diffraction structure formed in core surfaces Dielectric layer.The color and effect of light as needed select suitable rasterisation micro-structure, for having the diffraction of diffraction effect The production of piece.For example, pigment flakes can include grating frequency scope from every millimeter of about 400 grid stroke (ln/ millimeters) to 4000ln/ millimeters of diffraction grating microstructure, to generate extensive optical effect.
In one embodiment, prefabricated film includes micro-structural mark, such as symbol, is typically diameter about 0.5-20 Micron.In a specific embodiment, symbol is about 700 nanometers of diameter, and in another embodiment, symbol is that diameter is big About 15 microns.
Such as the micro-structure of symbol or grating is typically embossment or pours into a mould on the deposition substrate, and in the deposition of embossment Deposition film dielectric layer in substrate.At least the first film layer of the micro-structure on the substrate is deposited on substrate surface In, it is replicated with positive embossment or negative embossment.Then, the coating of film layer is separated from the deposition substrate, and is formed to use The micro-structural prefabricated film of core in encapsulation step 220.
Preferably, micro-structural core is formed by one or more dielectric substances, opaque when using to generate Irrealizable translucent dichroic pigments during metallic core.
Micro-structural dielectric piece can be mixed with the carrier of such as ink vehicle or coating link stuff, to form group Object is closed, such as ink or coating or its mixture paint in transparent carrier to be formed.The example of carrier includes polyvinyl alcohol, Polyvinyl acetate, polyvinylpyrrolidone, poly- (ethoxy ethylene), poly- (methoxy-ethylene), poly- (propylene) acid, poly- (propylene Amide), poly- (ethylene oxide), poly- (cis-butenedioic anhydride), hydroxyethyl cellulose, cellulose acetate, such as gum arabic and pectin is poly- (more Sugar), such as poly- (acetal) of polyvinyl butyral, such as polyvinyl chloride and polyvinylidene chloride (polyvinylene) are poly- (vinyl halide), such as poly- (diene) of polybutadiene, such as poly- (alkene) of polyethylene, such as poly-methyl methacrylate Poly- (acrylate) of ester, such as poly- (methacrylate) of polymethyl methacrylate, such as poly- (hydroxycarbonyl (oxycarbonyl) poly- (carbonate) of hydroxyhexen (oxyhexamethylene), such as poly- (ester) of poly terephthalic acid, Poly- (urethane), poly- (siloxanes), polythiaether (sulphides), poly- (sulfone), polyethylene nitrile (vinylnitriles), polyacrylonitrile (acrylonitriles), poly- (styrene), such as 2,5 dihydroxy-Isosorbide-5-Nitrae-phenylene vinylene (phenyleneethylene) Polyhenylene (phenylenes), poly- (amide), natural rubber, formaldehyde (formaldahyde) resin and other polymer.
In one embodiment, deposition substrate is subjected to embossment with diffraction grating pattern.Therefore, by by thin dielectric film Layer deposits to the tablet core that rasterisation surface is formed also has grating pattern in its one or both sides.Alternatively, dielectric Core can include more than one dielectric layer, before departing from the coating and being separated into individual prefabricated film, pass through On the deposition substrate deposition film layer and form the dielectric layer.
The micro-structural deposition substrate of micro-structure including such as diffraction grating and/or symbol can be by such as polychlorostyrene second The plastic material manufacture of alkene, makrolon, polypropylene and polyester-type G.It can be used for forming surface relief figure in deposition substrate The method of case is that those skilled in the art is well-known.It for example, can be by the nickel that heats its face contact under high pressure Embossing shim to carry out embossment to the surface of substrate.Other methods include the light to the plastic-substrates for abutting patterned surface It carves and moulds.
Various routine techniques can be used to deposit the layer of micro-structural tablet core, these technologies are for example using electron beam Or the physical vaporous deposition of resistance heating evaporation, reactive d.c.magnetron sputtering method, radio frequency (RF) magnetron sputtering method, magnetron sputtering Method, chemical vapour deposition technique (CVD), plasma enhanced chemical vapor deposition (PECVD) method etc..
Including those there is " height " refractive index (to be defined herein as being greater than about for the suitable material of dielectric tablet core 1.65) material and those there is the material of " low " refractive index (be defined herein as about 1.65 or smaller).
For dielectric core suitable high-index material example include zinc sulphide (ZnS), zinc oxide (ZnO), Zirconium oxide (ZrO2), titanium dioxide (TiO2), carbon (C), indium oxide (In2O3), indium tin oxide (ITO), tantalum pentoxide (Ta2O5), cerium oxide (CeO2), yttrium oxide (Y2O3), europium oxide (Eu2O3), such as the ferroso-ferric oxide of (II) and (III) valency (Fe3O4) and (III) valency di-iron trioxide (Fe2O3) ferriferous oxide, hafnium nitride (HfN), hafnium carbide (HfC), hafnium oxide (HfO2), lanthana (La2O3), magnesia (MgO), neodymium oxides (Nd2O3), praseodymium oxide (Pr6O11), samarium oxide (Sm2O3), three Aoxidize two antimony (Sb2O3), carborundum (SiC), silicon nitride (Si3N4), silica ((SiO), selenium arsenic trioxide (Se2O3), oxidation Tin (SnO2), tungstic acid (WO3) and their compositions etc..
Include silica (SiO for the low-index material of dielectric core2), aluminium oxide (Al2O3), such as be fluorinated Magnesium (MgF2), aluminum fluoride (AlF3), cerium fluoride (CeF3), lanthanum fluoride (LaF3) metal fluoride, sodium aluminium fluoride (for example, Na3AlF6Or Na5Al3F14), neodymium fluoride (NdF3), samaric fluoride (SmF3), barium fluoride ((BaF2), calcirm-fluoride (CaF2), fluorination Lithium (LiF) and their composition or any other low-index material with about 1.65 or more low-refraction.
Fig. 5 B show by encased core diffraction plate obtain have symmetric design by high index of refraction and low-refraction The manufacture for the micro-structural pigment flakes that material is formed.Preferably, core sheet is manufactured by the dielectric substance of individual layer, can be had There are high index of refraction or low-refraction.In the specific example shown in Fig. 5 B, with high-index material titanium dioxide to by dioxy The electric dielectric core for the low-refraction that SiClx is formed is packaged, so as to generate 3 layers (HLH) design.The encapsulation of titanium dioxide Layer is obtained by chemical vapour deposition technique, and this method uses titanium tetrachloride as precursor, in presence of water, in vapour form 200 DEG C about 1 it is small when carry out following reaction：
Titanium tetrachloride (TiCl4) (gas)+2H2O (gas) → titanium dioxide (TiO2)+4 hydrochloric acid (HCl)
Include the identical dielectric substance that can be used for core for the suitable material of encapsulated layer.By way of example, 5 layers (HLHLH) design can deposited layer of silicon dioxide by encapsulation, then deposited the titanium dioxide core of layer of titanium dioxide Heart prefabricated film obtains.In another example, by using continuous titanium dioxide layer, silicon dioxide layer and titanium dioxide layer envelope The silica diffraction core sheet of low-refraction is filled to obtain 7 layers of design (HLHLHLH).
In the art, it is known that for example alternate high index of refraction and the full dielectric design of low-index layer can be provided and taken Certainly in layer thickness optical variable effect.
Alternatively, encapsulated layer can include one or more metal absorption layers, can be due to the interference of light so as to be formed The inter metal dielectric design of the multilayer of gamut effect is provided.By way of example, formed by silica and use such as W, Ti, The dielectric core of the Metal absorption body encapsulation of Cr, Mo forms and can provide gamut effect due to the metallic dielectric stack Micro-structural pigment.The optical design of the high index of refraction dielectric core encapsulated using Metal absorption body generates similary tool There are very gay colours but the pigment of less gamut effect.Can also use Metal absorption body encapsulation alternately low-index layer and The Multi-layer design of high refractive index layer, such as HLH, LHL, HLHLH, LHLHL.If micro-structure is diffraction grating, pigment can be by Optical variable effect is provided in diffraction interference.In the case where micro-structure includes mark, pigment can be used for anti-fake purpose, because Mark provides hidden security feature and color change-apparent security feature.
In diffraction plate, encapsulated layer is as conformal with the micro-structure of core as possible, is regarded with generating required based on diffraction Feel optical effect, therefore we use fluidized-bed chemical vapor deposition (FBCVD) technology.Chemical vapor deposition (CVD) causes Single-layer or multi-layer coating is deposited on core granule surface；The material of deposition is formed from gaseous state, liquid or solid precursor. CVD technology obtains the conformal encapsulating film for the surface micro-structure for replicating core sheet.The efficiency of this process depend on particle and Contact between film precursor surface.The technical solution for allowing the good contact between particle and gaseous precursors is to use fluid bed skill Art.
FBCVD methods are based on the chemical reaction between precursor and reactant.In most cases, in the association of reactant It helps down, precursor is aoxidized, so as to obtain oxide covering on particle.Respective nitridation can be formed by providing the reactant of nitrogen and carbon Object and carbide coating.It can be used for the mixture such as carbonitride of the reactant of the deposition of compound (carbonitrides), oxycarbide (oxycarbides), nitrogen oxides (oxinitrides) and carbon nitrogen oxide (oxicarbonitrides).Precursor and reactant can be gas, the form of liquid or solid material.Preferably, with it is preceding Body flows opposite direction and provides reactant.Preferably, this method includes the use of the non-reactive fluidizing gas for hybrid particles.Have Sharp ground, chemical vapour deposition technique can carry out at atmosheric pressure.But depending on core sheet material and to be deposited it is thin Film can use low pressure or plasma to activate.
A variety of geometries can be used for fluidized-bed reactor；The fluid bed should meet due to grain fluidized and chemical gas The limitation that phase sedimentation generates.The fluid bed can the reaction gas precursor suitable for grain type to be processed heat or wait It works under gas ions activation condition.
The optical effect of special effects pigment with film and diffraction interference combination is to be highly dependent upon core diffraction face Expect the smooth duplication of the diffraction micro structural of prefabricated film, become FBCVD technologies for manufacturing the spy with optical diffraction characteristic The perfect solution of different effect pigment.
With reference to figure 6, fluidized-bed reactor can be hydrostatic column 100, have to keep particle 180 and in container Transverse area be uniformly distributed the Porous Base of air-flow or perforation plate 170, it is uniform so as to be obtained in the particle of fluid bed It suspends.In operation, the gas provided by fluid bed moves, and particle is supported in part so that and the volume of particle expands, and Diffusion becomes fluid everywhere in a reservoir.In fluid bed, air-flow is turbulent flow, obtains good quality and biography between particle Heat, these are very important for the uniform encapsulation of the chemical vapor deposition of pigment flakes.
Compared with other such as physical vapour deposition (PVD) (PVD) deposition techniques, FBCVD methods provide a variety of advantages.PVD master By coating material deposition to the surface of the particle towards flow of vapor, and FBCVD provides the uniform fold of particle.With PVD It compares, FBCVD provides higher growth rate not only due to its three-dimensional growth characteristics, also on micro-structural core granule More good uniformity and conformal performance are provided for encapsulated layer.This is very important in the encapsulation of diffractive pigment piece, this It is because the surface of the piece has a groove of symmetric arrays, the groove is with can be from several microns of low-frequency grating to high-frequency Grating down to 250 nanometers of spacing, i.e. grating has the frequency range of the lines per millimeter from 400 to 4000.
The reactor used in our experiment is manufactured by quartz.One example of fluidized-bed reactor is as in Fig. 6 Shown.The reactor has dismountable top surface (not shown), has for instrument, gas and liquid introducing and volume The access interface of outer vibration.Arrow 110 shows such as nitrogen, ammonia, water, carbon dioxide, hydrogen and/or for injection The passage of the introducing of the reactant gas of the Liquid precursor of above-mentioned gas.Alternatively, argon gas, helium or other inert gases are drawn Enter, to dilute or transmit reactant.Precursor and/or reactant can be the forms of liquid or solid.Liquid or solid can be It is heated in container and (is referred to as the bubble for Liquid precursor)；Inert gas is introduced in container, to shift the steam of precursor. In general, solid has low-vapor pressure, and must be heated at a higher temperature using stove.Fluidization conditions can basis The visual observation of fluid bed adjusts flow velocity by using flow controller and is changed.Top surface can also have for example mechanical The vibrating device 160 of vibrator and the exhaust apparatus of such as waste gas filter or washer；Arrow 120 is shown from exhaust apparatus Waste gas flow direction.Instrument 130 can include thermocouple and for extracting particle to control the extraction system of its optical property and its Its sensor device.
According to the physical property (density, vapour pressure etc.) of coating precursor, in the aluminium oxide that the bottom of reactor passes through sintering Grid 170, the precursor 150 can be introduced into upstream with fluidizing gas (argon gas, nitrogen, helium etc.).Into before reactor Allow to control the fluidization conditions of fluid bed to the independent control of fluidizing gas and precursor gases.Precursor can come from bubble, Such as silicon tetrachloride, titanium tetrachloride, trichlorosilane (SiHCl3) precursor or from different precursor vapor sources, such as six carbonyls Tungsten (W (CO)6), six carbonyl nickels (Ni (CO)6), for the low vapor pressure solid precursor of W and Ni metals or compound, can distinguish It is heated at high temperature using enclosed furnace.Fluidizing gas can be provided from for the flow controller of fluidizing gas.Preceding In the case that body has low-vapor pressure, such as some include (ethyl orthosilicate) TEOS and 2,3,5- Triiodobenzoic acids (TIBA) Organic metal, it can use metering liquid syringe by being introduced directly at the top of the reactor；In this case, lead to The bottom for crossing the reactor provides reactant and fluidizing gas.
FBCVD reactors can work under conditions of heat or plasma activation.For hot activation, cylinder can be passed through Type resistance furnace 150 carries out external heating or uses graphite base (susceptor) and external radio-frequency (RF) line of induction Circle carries out internal heating.External Rf coils are can also use, for the plasma of the chemical vapor deposition of plasmaassisted Activation, the advantage with nonequilibrium plasma, the nonequilibrium plasma can lower temperature activate gaseous state object Kind.In some cases, FB reactors can have the vacuum pump for low-pressure chemical vapor deposition (LPCVD)；Vacuum pump can Using as or exhaust apparatus a part；Filter can be used to avoid damage vacuum pump.
Possible precursor includes metal halide (chloride, iodide and bromide).Hydrogen halide is hydrolytic process In by-product.
FBCVD based on following can be chemically reacted：
Titanium tetrachloride (TiCl4)+water (H2O) → titanium dioxide (TiO2)+hydrochloric acid (HCl)
- for titanium dioxide deposition and
Silicon tetrachloride (SiCl4)+water (H2O) → silica (SiO2)+hydrochloric acid (HCl)
- for the deposition of silica.
Using oxygen or ozone water can be replaced to form oxide.In order to change oxidizing condition, and avoid in gas phase Rather than the homogeneous coring on the surface of piece, H can be used2And CO2Mixture replace water or oxygen.In this case, gas The chemical reaction of body can be：
H2+CO→H2O+CO
Other possible precursors can be used for SiO2Such as trichlorosilane (the SiHCl of encapsulation3) alkyl silane.In addition, In some cases, original precursor reaction in the gas phase, to form other chemical gas, such as titanium trichloride, when using When titanium tetrachloride is used for the deposition of titanium dioxide as precursor, titanium trichloride is generally observed in the gas phase.
Such as aluminium chloride AlCl3It can be used for depositing their own oxide with other chlorides of zirconium chloride.
With N2Or NH3The reaction of reactant generates corresponding metal nitride.With providing carbon (such as methane) for reaction The reaction of reactant gas results in the formation of metal carbides.
Halide can be used for providing oxygen, the reactant gas combination of nitrogen and/or carbon, with deposition oxide, nitrogen Compound, such as carbide or nitrogen oxides, carbonitride, oxycarbide (oxycarbides) and carbon nitrogen oxide (oxycarbonitrides) compound combination.
Alkoxide precursor can contain enough oxygen, to form oxide without additional oxygen.It is but usually used O2, the possibility that carbon is introduced in sedimentary is minimized.Water can be used to replace oxygen as reactant, to reduce reaction Temperature.
Example for the Organometallic precursor of silica deposition includes ethyl orthosilicate (TEOS) silicic acid ([Si (OC2H5) 4]), dimethyl diethoxysilane (DMDEOS) dimethyl diethoxysilane ([(CH3) 2SI (OC2H5) 2]), Hexamethyldisiloxane (HMDSO) hexamethyldisiloxane ([(CH 3) 3SiOSi (CH3) 3]), tetramethyl disiloxane (TMDSO), 1,1,3,3- tetramethyl disiloxane ([(CH3) 2HSiOSiH (CH3) 2)]), trichloroethyl silane (ETEOS) second Ethyl triethoxy silicane alkane ([C2H5Si (OC2H5) 3]), trimethylethoxysilane (TMEOS) trimethylethoxysilane ([(CH3)3SiOC2H5)])。
Example for the Organometallic precursor of deposition of titanium oxide includes tetraethyl titanate, isopropanol and the tert-butyl alcohol.
The decomposition of titanium isopropanol titanium tetraisopropylate (Ti iso-propoxide Ti { OCH (CH 3) 2 } 4) can be used for FBCVD：
Titanium tetraisopropylate Ti { OCH (CH3) 2 } 4 → titanium dioxide (TiO2)+propane (C3H8)+propyl alcohol (C3H7OH)+water is high In 450 DEG C.
Ethanol tantalum (Ta (OC2H5) 5) can be used together with oxygen, for another high-index material Ta2O5Life It is long.
Triisobutyl aluminium (TIBA) is the liquid of igniting decomposed in the temperature higher than 200 DEG C on aluminium and isobutene, and It can be used for the alundum (Al2O3) layer for depositing medium refractive index (refractive index n is about 1.65).
It is worth noting that, the encapsulated layer of deposition can be fully oxidized (such as metal hydroxides), and because This may need the high annealing in the range of 400 DEG C to 900 DEG C, to reach the stoichiometry of needs.
Such as other precursors of carbonyl are decomposed in relative low temperature, and deposition oxide.By way of example, iron carbonyl can be used Iron Fe (CO)5Carry out deposition of iron oxide：
2Fe(CO)5+O2→Fe2O3+5CO2
Fig. 7 A-10 show dielectric diffraction plate, by providing micro-structural silica core to fluid bed, and And micro- knot in the fluid bed is encapsulated by using the chemical vapour deposition technique of the titanium tetrachloride precursor reacted with vapor The dielectric core of structure encapsulates the titanium dioxide encapsulated layer of the micro-structural dielectric core to form the electricity with formation Medium diffraction plate.
Fig. 7 A-7D are shown under the various amplification factors from 250 times (Fig. 7 A) to 25000 times (Fig. 7 D) using scanning electricity The microphoto for the diffractive pigment piece that sub- microscope (SEM) obtains；Microphoto in Fig. 7 A-7C is shown in next width picture The middle small rectangle further amplified.The piece has symmetrical three layers of TiO2/SiO2/TiO2Structure is sealed by using titanium dioxide The micro-structural single-layer core formed by silica is packaged by dress layer forms the structure.The core be shaping 25 × 25 microns of prefabricated film has the diffraction grating of 1400l/mm frequencies.
Fig. 8 A-8C show the cross sectional image of the typical case chip shown in such as Fig. 7 A-7D, for by using The ultrathin sectioning of transmission electron microscope (TEM) with 25000 times of amplification factor analyzes the image.Titanium dioxide The thickness of silicon core is about 120nm；The titanium dioxide layer of the encapsulation has about 30 nanometers of thickness, and preferably with core The micro-structure of piece is very conformal.
Fig. 9 shows the image at the piece edge obtained with scanning transmission electron microscope (STEM)；It shows to come with Figure 10 From energy dispersion X-ray spectrometer (EDS) elemental analysis of the spectrum of the marked region 1,2,3 and 4 in STEM images.Table 1 with The form of atomic percent shows corresponding quantitative elemental analysis.Chlorine is in TiOxLayer is detected.V signal is in most of Ti films In be found.Ti and O2Presence confirm encapsulation titanium dioxide layer essence.
Table 1
Spectrum O Si Cl Ti V
Spectrum 1 23.45 7.69 67.13 1.72
Spectrum 2 30.00 7.34 60.97 1.69
Spectrum 3 53.20 40.37 6.44
Spectrum 4 57.08 37.50 5.42
In the presence of titanium tetrachloride precursor, it is packaged using fluidized-bed chemical vapor deposition method.It is however possible to use Other precursors.By way of example, such as the organic metal of titanium-isopropanol (TI (OC3H7) 4) can be used for titanium dioxide The deposition of encapsulated layer.
In another embodiment, full dielectric piece can have more than one encapsulated layer.For example, alternating is passed through By titanium dioxide, silica and titanium dioxide deposition to the micro-structural core of silica symmetrical set obtain 7 layers Meter.The silicon halide precursors such as SiCl of SiCl4 can be used4Or use such as tetraethoxysilane TEOS (Si (OC2H5) 4 Or hexamethyldisiloxane HMDSO (Si2O(C2H3)3) deposit SiO2Layer；Titanium dioxide layer and core can be as described above by shapes Into.
Alternatively possible design can originate in high refractive index layer (such as titanium dioxide), the dioxy deposited with post package SiClx and titanium dioxide.Silica and titanic oxide material have the advantage compatible with cosmetic industry.However, it is possible to complete The other materials with high and low-refraction are used in dielectric design.
Fluidized-bed chemical vapor deposition (FBCVD) and chemical precipitation are to coat two kinds of skills being more suitable for of core granule Art.But such as the wet chemistry method disclosed in the patent of the U.S. the 6th, 241,858 need it is extensive between solid core lamination Separation so that reaction solution can to the greatest extent can be mostly contacted with the surface of piece.In addition, it needs the piece after dry and drying steps Disintegrate (disagglomeration).As similar techniques, FBCVD avoids these additional steps.Due to mass transfer and biography Heat and solid mixing, FBCVD technologies avoid and the relevant agglomeration problems of wet chemistry methods.Advantageously, using FBCVD skills The layer and the surface micro-structure of diffraction core sheet of art coating are completely conformal, so that piece has higher performance.When conventional method is used When micro-structural piece is coated, the relatively low conformal performance of encapsulated layer causes the diffraction as caused by the micro-structure of the diffractive pigment Effect degenerating or even losing completely.Conformal layer by the wet chemistry method of chemical precipitation or any other form all very It is difficult to obtain, on the contrary, often generating the coat of not conformal planarization.In addition, FBCVD technologies can be used for high metal The deposition of absorbed layer --- metal layer i.e. containing high percentage ---, and general chemical precipitation cannot generate high percentage and contain The metal layer of amount.

Claims (17)

1. a kind of method for forming micro-structural pigment flakes, the described method includes：
Single dielectric layer is deposited in micro-structural substrate, to form single micro-structural dielectric layer；
The single micro-structural dielectric layer is separated from the micro-structural substrate；
The single micro-structural dielectric layer is crushed, to form multiple micro-structural dielectric cores；
By chemical vapor deposition, with the multiple micro- knot of one or more additional dielectric layer encapsulation in fluid bed The dielectric core of structure.
2. the method as described in claim 1, wherein the chemical vapor deposition is reacted including hot activation.
3. the method as described in claim 1, wherein the chemical vapor deposition is activated including plasma.
4. the method as described in claim 1, wherein encapsulating the multiple micro-structural dielectric core is included by described The bottom of fluid bed provides fluidizing gas.
5. the method as described in claim 1, wherein encapsulating the multiple micro-structural dielectric core is included from upper direction The fluid bed provides precursor.
6. the method as described in claim 1, wherein encapsulating the multiple micro-structural dielectric core is included by described The bottom of fluid bed provides precursor.
7. the method as described in claim 1, wherein encapsulate the multiple micro-structural dielectric core include with precursor The opposite direction in flow direction reactant is provided.
8. the method as described in claim 1, wherein the chemical vapor deposition includes the use of Organometallic precursor.
9. the method as described in claim 1, wherein the fluid bed includes Porous Base or perforation plate.
10. the method as described in claim 1, wherein reactant are water.
11. the method as described in claim 1, wherein each in the multiple micro-structural dielectric core includes position Grating in its surface.
12. method as claimed in claim 11, wherein each in one or more of additional dielectric layers and position Grating in the surface of each of the multiple micro-structural dielectric core is conformal.
13. method as claimed in claim 11, wherein each duplication in one or more of additional dielectric layers The grating in the surface of each of the multiple micro-structural dielectric core.
14. the method as described in claim 1, wherein the micro-structural pigment flakes illustrate it is multiple micro-structural by being located at Dielectric core at least one surface in grating and the diffraction effect that provides of one or more additional dielectric layers.
15. the method as described in claim 1, wherein the micro-structural dielectric core is formed by low-index material.
16. the method as described in claim 1, wherein one or more of additional dielectric layers are by high-index material shape Into.
17. the method as described in claim 1, in addition to the deposit absorbent on one or more of additional dielectric layers Layer.
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